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CHAPTER I.

The Electrical Double Layer and Its Structure


Zbigniew Stojek

I.1.1
Introduction
At any electrode immersed in an electrolyte solution, a specific interfacial region
is formed. This region is called the double layer. The electrical properties of such
a layer are important, since they significantly affect the electrochemical mea-
surements. In an electrical circuit used to measure the current that flows at a
particular working electrode, the double layer can be viewed as a capacitor.
Fig. I.1.1 depicts this situation where the electrochemical cell is represented by
an electrical circuit and capacitor Cd corresponds to the differential capacity of

Fig. I.1.1. A simple electronic scheme equivalent to the electrochemical cell. Ru resistance un-
compensated in the regular three-electrode system; Cd differential capacity of the double
layer; Rf resistance to faradaic current at the electrode surface, RW solution resistance com-
pensated in the three-electrode system
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the double layer. To obtain a desired potential at the working electrodes, the dou-
ble-layer capacitor must be first appropriately charged, which means that a ca-
pacitive current, not related to the reduction or oxidation of the substrates, flows
in the electrical circuit. While this capacitive current carries some information
concerning the double layer and its structure, and in some cases can be used for
analytical purposes, generally, it interferes in electrochemical investigations. A
variety of ways are used in electrochemistry to depress, isolate or filter the ca-
pacitive current.
Although many models for the double layer have been published in the liter-
ature, there is no general model that can be used in all experimental situations.
This is because the double-layer structure and its capacity depend on several pa-
rameters such as: electrode material (metals, carbons, semiconductors, elec-
trode porosity, the presence of layers of either oxides or polymeric films or other
solid materials at the surface), type of solvent, type of supporting electrolyte, ex-
tent of specific adsorption of ions and molecules, and temperature.
The composition of the double layer influences the electron transfer rate (see
Chap. I. 3.1.5). Some ions and molecules specifically adsorbed at the electrode
surface enhance the rate of the electrode process. In such a situation we talk
about heterogeneous electrocatalysis. On the other hand, there are numerous
compounds which, after adsorption, decrease the electron transfer rate and
therefore are simply inhibitors. Some surface-active compounds can be very
strongly adsorbed. This may lead to the total isolation of the electrode surface
and, finally, to the disappearance, or substantial decrease, of the voltammetric
peaks or waves.
An imposition of a potential from an external source (potentiostat/voltam-
mograph) to a metallic electrode results in generation of a charge, sM , on the
metal, and a charge sS in the solution. The charge at the electrode is related di-
rectly to the interfacial (double layer) capacity or capacitance. There are two
ways to describe the capacity of an electrode:
– the differential capacitance, Cd , which naturally is at the minimum for the po-
tential of zero charge, and which is represented by Eq. (I.1.1):
∂sM
Cd = 8 (I.1.1)
∂E
– and the integral capacitance, Ci , described by Eq. (I.1.2).
sM
Ci = 87 (I.1.2)
E – Es = 0
The excess charge on the metallic electrode, sM , is a function of the electrode po-
tential. The simplest equation that describes the charge on the metal is given for
mercury electrodes. This is because the excess charge strongly affects the surface
tension of mercury, and the latter can be easily measured experimentally. One
simple method to measure the surface tension vs potential is to measure the
drop time of a mercury-dropping electrode immersed in an electrolyte solution.
The surface tension of mercury plotted vs potential usually gives a parabolic
I.1 The Electrical Double Layer and Its Structure 5

curve. The maximum of this curve is located at the potential of zero charge,
Es = 0 , since:
∂g
– sM = 5 (I.1.3)
∂E
and the derivative of the surface tension equals 0 at the maximum. The differen-
tial capacity, Cd , reaches its minimum also at the potential of zero charge, a fact
that can be concluded from a simple inspection of Eq. (I.1.1).

I.1.2
Double-Layer Models

The concept of the existence of the double layer at the surface of a metal being
in contact with an electrolyte appeared in 1879 (Helmholtz). That first theoreti-
cal model assumed the presence of a compact layer of ions in contact with the
charged metal surface. The next model, of Gouy and Chapman, involves a diffuse
double layer in which the accumulated ions, due to the Boltzmann distribution,
extend to some distance from the solid surface. In further developments, Stern
(1924) suggested that the electrified solid-liquid interface includes both the
rigid Helmholtz layer and the diffuse one of Gouy and Chapman. Specific ad-
sorption of ions at the metal surface was pointed out by Graham in 1947. In con-
secutive developments, the role of the solvent has been taken into account (Par-
sons 1954; Bockris 1963). It soon became clear that in dipolar solvents, such as
water, the dipoles must interact with the charged metal surface. It is also worth
noting here that these interactions are promoted by the high concentration of
the solvent, which is usually at least several moles per liter, and, in particular, for
water it is around 55.5 M. In his theory, Parsons recognized that the dielectric
constant of the solvent in the compact layer of adsorbed molecules is much
lower compared to the outer region and approaches the limiting Maxwell value.
A detailed description of the double-layer models mentioned above can be
found in the literature [1–4].
A classic, simplified model of the double layer formed at the metal electrode
surface is presented in Fig. I.1.2. There is a layer of adsorbed water molecules on
the electrode surface. Since it has been assumed that there is excess of negative
charge at the metal phase, the hydrogen atoms of adsorbed water molecules are
oriented towards the metal surface. However, it is not a prerequisite that all wa-
ter molecules at a particular electrode potential and the corresponding excess
charge have the same orientation. For excess of positive charge at the metal sur-
face, the dipoles of water will have different orientation. A specifically adsorbed
large neutral molecule is also shown in Fig. I.1.2. This molecule has removed
some water molecules from the surface. On the other hand, a hydrated cation
present at the surface has not removed surface water, and therefore cannot be
considered as specifically adsorbed.
Two planes are usually associated with the double layer. The first one, the in-
ner Helmholtz plane (IHP), passes through the centers of specifically adsorbed
ions (compact layer in the Helmholtz model), or is simply located just behind the
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Fig. I.1.2. General representation of the double layer formed at the metal–electrolyte interface

layer of adsorbed water. The second plane is called the outer Helmholtz plane
(OHP) and passes through the centers of the hydrated ions that are in contact
with the metal surface. The electric potentials linked to the IHP and OHP are
usually written as Y2 and Y1 , respectively. The diffuse layer develops outside the
OHP. The concentration of cations in the diffuse layer decreases exponentially vs
the distance from the electrode surface. The hydrated ions in the solution are
most often octahedral complexes; however, in the figure, they are shown as tetra-
hedral structures for simplification.
The change in the electric potential within the double layer is illustrated in
Fig. I.1.3. It is assumed that the electrode is charged negatively. The electric po-
tential, fM , is virtually constant throughout the metallic phase except for the lay-
ers of metal atoms located next to the solution, where a discontinuity in the
metal structure takes place and the wave properties of the electron are exposed
(the jellium model [1, 3]). This effect is much stronger in semiconductor elec-
trodes, where the accessible electronic levels are more restricted [5].
At carbon electrodes, which are widely used in electrochemistry, the double
layer develops too; however, these electrodes have some specific interfacial prop-
erties. The two main types of carbon electrodes: glassy carbon and highly ori-
ented pyrolitic graphite (HOPG) and the recently introduced boron-doped dia-
mond, differ much in the bulk and the surface structure. They also differ in elec-
trochemical activity. Particularly large differences exist for the two surfaces of
I.1 The Electrical Double Layer and Its Structure 7

Fig. I.1.3. Potential profile in the double layer formed at a metallic electrode charged nega-
tively

highly oriented pyrolitic graphite: the basal (hexagonal) and the edge one.At the
edge plane, the electrode processes are usually much faster. An additional im-
portant factor for the electron transfer rate is the presence of oxygen at the sur-
face. Oxygen easily chemisorbs on sp2 carbon present in graphitic materials.
This leads to the formation of many functional groups, mainly carbonyl, pheno-
lic and carboxylate, and to an increase in the rate of the electrode processes. To
reverse the chemisorption of oxygen, and to obtain, reproducibly, oxygen-free
surfaces, is not easy. Neither is it easy to keep the surface oxygen-to-carbon ra-
tio constant in the consecutive experiments. A positive aspect of the presence of
the functional groups at the graphitic surfaces is that they make the chemical
modification of the electrodes easier.
Details of the properties of carbon electrodes can be found in the litera-
ture [6].

I.1.3
Thickness of the Electric Double Layer
The thickness of the double layer is usually given as being approximately 1.5k –1,
where k –1 is the Debye-Hückel length:

k –1 = (eeokT/2c 0 z 2i e 02)1/2 (I.1.4)

where c 0 is the bulk z:z electrolyte concentration, e is the relative dielectric per-
mittivity of the solvent, eo is the permittivity of the vacuum, k is the Boltzmann
constant, T is the temperature, z is the ion charge and e0 is the elementary charge.
For z = 1, the approximate k –1 values calculated for electrolyte concentrations of
1 ¥ 10–3, 1 ¥ 10–5 and 1 ¥ 10–7 M are 10 nm, 100 nm and 1 mm, respectively. The
thickness of the double layer also depends on the potential: the larger the dif-
ference between the electrode potential and the potential of zero charge (the po-
tential at which the excess charge on the electrode equals zero), the smaller is the
Debye-Hückel length.
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I.1.4
Recent Developments
There is still much to do to be able to predict the behavior and the capacitance
of the double layer in the entire available potential window and under all
conditions. The introduction of rigorous theories that can take into account the
various chemical and electrochemical properties of electrode materials, the
specific adsorption of ions and neutral molecules and the dynamics of adsorbed
solvent molecules and other adsorbates is not trivial. In consequence, there
is still no satisfactory agreement between the experimental and theoretical
data regarding capacitance of the double layer. Hopefully, the new experimental
techniques, such as atomic force and scanning tunneling microscopies [7],
and scanning electrochemical microscopy [8], will allow electrochemists to
learn more about the structure of the double layer at the atomic level. On the the-
oretical side, the new digital methods of calculations provide a possibility to
simulate, in time, all the changes within the double layer. The recent progress in
the research on the solid-liquid electrochemical interfaces is given in, e.g., [9]
and [10].

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